EP1565502B1 - Butene-1 copolymers and process for their preparation - Google Patents
Butene-1 copolymers and process for their preparation Download PDFInfo
- Publication number
- EP1565502B1 EP1565502B1 EP03779841A EP03779841A EP1565502B1 EP 1565502 B1 EP1565502 B1 EP 1565502B1 EP 03779841 A EP03779841 A EP 03779841A EP 03779841 A EP03779841 A EP 03779841A EP 1565502 B1 EP1565502 B1 EP 1565502B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- butene
- ethylene
- copolymers
- propylene
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229920001577 copolymer Polymers 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 title claims description 17
- 230000008569 process Effects 0.000 title claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000005977 Ethylene Substances 0.000 claims abstract description 49
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 22
- 238000003780 insertion Methods 0.000 claims abstract description 12
- 230000037431 insertion Effects 0.000 claims abstract description 12
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 9
- 230000009257 reactivity Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 30
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 23
- 229920001038 ethylene copolymer Polymers 0.000 claims description 12
- -1 alkylaluminum compound Chemical class 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 239000011949 solid catalyst Substances 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 4
- 230000014509 gene expression Effects 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 230000000707 stereoselective effect Effects 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 238000002076 thermal analysis method Methods 0.000 claims description 2
- 125000005498 phthalate group Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 23
- 229910003074 TiCl4 Inorganic materials 0.000 description 12
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 235000011147 magnesium chloride Nutrition 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- UVGKQRAGAYVWQV-UHFFFAOYSA-N 2,3-dimethylbutan-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C(C)C UVGKQRAGAYVWQV-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229910010062 TiCl3 Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical class Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KCASYFCAUMELFB-UHFFFAOYSA-N BPPB Chemical compound BPPB KCASYFCAUMELFB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000006653 Ziegler-Natta catalysis Methods 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000254 composite pulse decoupling sequence Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001969 wideband alternating-phase low-power technique for zero residual splitting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
Definitions
- the present invention relates to butene-1 copolymers containing up to 40% by mol of ethylene and/or propylene derived units, and to a process for their preparation.
- butene-1 copolymers are well known in the art and have a wide range of applicability.
- butene-1 copolymers with a low content of comonomer (1-3%by mol) are generally characterized by good properties in terms of pressure resistance, creep resistance, impact strength and can be used in the manufacture of pipes for replacing the metal pipes.
- One of the key aspects for their application in the pipe sector is the excellent balance between flexibility and rigidity that they must have in order to combine easy pipe workability and mechanical resistance.
- butene-1 copolymers with a higher content of comonomer can be used for example as components of blends with other polyolefin or polymeric products, in order to modulate particular properties such as sealing strength, flexibility and softness of the plastic materials.
- the butene-1 copolymers can be prepared by copolymerizing butene-1 in the presence of TiCl 3 -based catalyst components together with diethylaluminum chloride (DEAC) as cocatalyst.
- the copolymers obtained by this process generally do not show satisfactory properties because of the substantially non-random distribution of the comonomer in the polymer chain.
- the butene-1 copolymers prepared with these catalysts have a high content of catalyst residues (generally more than 300 ppm of Ti) which lowers the properties of the polymers making it necessary a deashing step.
- Butene-1/propylene copolymers and a method for their preparation are described in EP-A-353319 .
- the said copolymers are obtained by polymerizing the monomers in the presence of a stereospecific catalyst comprising a solid component comprising a Ti compound and a phthalate supported on MgCl 2 ; an alkylaluminum compound and a heterocyclic compound, in particular 1,8-cineole, as external electron-donor compound.
- a stereospecific catalyst comprising a solid component comprising a Ti compound and a phthalate supported on MgCl 2 ; an alkylaluminum compound and a heterocyclic compound, in particular 1,8-cineole, as external electron-donor compound.
- the same catalyst system was used to prepare butene-1/ethylene copolymers.
- Butene-1/ethylene copolymers have been disclosed also in PCT/EP 02/06574 by using a catalyst based on metallocene compounds.
- this kind of copolymers there is the presence of regioerrors due to 4,1 insertions of the butene-1 units.
- This kind of regioerrors in the polymer chain makes more difficult to tune the comonomer content of the copolymer because a 4,1 insertion can be considered equivalent to two consecutive ethylene units in the polymer chain.
- butene-1 copolymers having a complex of properties making them suitable for the various applications.
- this need is satisfied by butene-1 copolymers having a particular balance between isotacticity and distribution of the comonomer together with absence of 4,1 insertions of the butene-1 units.
- butene-1 copolymers containing up to 40% by mol of ethylene and/or propylene derived units, characterized by the following properties, determined as described on pages 10 to 12:
- copolymers object of the present invention are endowed with the following features:
- the content of (mmmm) is >99% in correspondence of r1 ⁇ r2 ⁇ 1.
- the copolymers of the present invention preferably have a Polydispersity Index measured according to the method specified below, ranging from 2 to 15; more preferably ranging from 3 to 10 and in particular in the range 4-8.
- the content of ethylene or propylene derived units in the copolymers of the present invention preferably ranges from 0.1 to 35% by mol, more preferably from 0.5 to 30% by mol.
- copolymers having a content of ethylene or propylene lower than 3% by moles and in particular lower than 2.5% can be particularly suitable for use in the pipe sector.
- ethylene is a preferred comonomer.
- Butene-1 copolymers having a comonomer content in the range of 2-15% by moles and preferably 3-12%, can be suitable also for the preparation of polymer compositions for use in low seal initiation temperature or fiber applications.
- butene-1 copolymers according to the present invention generally become amorphous when their comonomer content, in particular when the comonomer is ethylene, is 12% by mol or higher. At these value of comonomer content in fact, a melting point is no longer detectable by carrying out thermal analysis. Moreover, the amount of fractions soluble in xylene at 0°C becomes greater than 95%. Said specific copolymers also proved to be very soft as shown by a Shore A value of lower than 70 and in certain cases lower than 50. In view of these properties, these copolymers can be used in particular as components of polymeric compositions for use in applications where a certain level of softness is required.
- (A) can be present in an amount ranging from 10 to 90% and (B) in an amount ranging from 90% to 10%.
- the component (B) comprises an olefin (co)polymer.
- the component (B) can be selected from ethylene containing (co)polymers, propylene containing (co)polymers and from their mixtures.
- polymer compositions comprising:
- said ⁇ -olefin is butene-1.
- (B) is selected from (a) a propylene copolymer containing both ethylene and butene-1 wherein the content of ethylene is from 1 to 10% and the content of butene-1 is from 1 to 10% and (b) a propylene copolymer containing from 2 to 15% by mol of butene-1.
- Said compositions which are particularly useful in applications where a low seal initiation temperature (SIT) is required, show better performances, in terms of SIT and mechanical properties, with respect to the compositions in which butene-1 copolymers of the prior art are used.
- SIT seal initiation temperature
- these formulations comprise:
- the ethylene polymer can be an ethylene homopolymer or copolymer.
- it can be selected from branched ethylene homo or copolymers obtained through high pressure high temperature radical initiated polymerization (LDPE), linear ethylene homo or copolymers with alpha-olefins having from 4 to 10 carbon atoms (HDPE or LLDPE) obtained through the use of the well known coordination catalysts such as the Ziegler-Natta catalysts or mixtures thereof.
- LDPE high pressure high temperature radical initiated polymerization
- HDPE or LLDPE linear ethylene homo or copolymers with alpha-olefins having from 4 to 10 carbon atoms
- the well known coordination catalysts such as the Ziegler-Natta catalysts or mixtures thereof.
- compositions containing the copolymers of the invention have shown better performances, in terms of peel performances, with respect to the compositions in which butene-1 copolymers of the prior art are used.
- the butene-1 copolymers of the present invention can be prepared by polymerization of the monomers in the presence of a stereospecific catalyst comprising (A) a solid component comprising a Ti compound and an internal electron-donor compound supported on MgCl 2 ; (B) an alkylaluminum compound and, optionally, (C) an external electron-donor compound.
- a stereospecific catalyst comprising (A) a solid component comprising a Ti compound and an internal electron-donor compound supported on MgCl 2 ; (B) an alkylaluminum compound and, optionally, (C) an external electron-donor compound.
- Magnesium dichloride in active form is preferably used as a support. It is widely known from the patent literature that magnesium dichloride in active form is particularly suited as a support for Ziegler-Natta catalysts. In particular, USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis.
- magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.
- the preferred titanium compounds used in the catalyst component of the present invention are TiCl 4 and TiCl 3 ; furthermore, also Ti-haloalcoholates of formula Ti(OR) n-y X y , where n is the valence of titanium, X is halogen, preferably chlorine, and y is a number between 1 and n, can be used.
- the internal electron-donor compound is preferably selected from esters and more preferably from alkyl, cycloalkyl or acryl esters of monocarboxylic acids, for example benzoic acids, or polycarboxylic acids, for example phthalic or succinic acids, the said alkyl, cycloalkyl or aryl groups having from 1 to 18 carbon atoms.
- Examples of the said electron-donor compounds are diisobutyl phthalate, diethylphtahalate and dihexylphthalate.
- the internal electron donor compound is used in molar ratio with respect to the MgCl 2 of from 0.01 to 1 preferably from 0.05 to 0.5.
- the preparation of the solid catalyst component can be carried out according to several methods.
- the magnesium dichloride in an anhydrous state and the internal electron donor compound are milled together under conditions in which activation of the magnesium dichloride occurs.
- the so obtained product can be treated one or more times with an excess of TiCl 4 at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared.
- the product obtained by co-milling the magnesium chloride in an anhydrous state, the titanium compound and the internal electron donor compound is treated with halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene or dichloromethane. The treatment is carried out for a time between 1 and 4 hours and at temperature of from 40°C to the boiling point of the halogenated hydrocarbon.
- the product obtained is then generally washed with inert hydrocarbon solvents such as hexane.
- magnesium dichloride is pre-activated according to well known methods and then treated with an excess of TiCl 4 at a temperature of 80 to 135°C which contains, in solution, an internal electron donor compound.
- the treatment with TiCl 4 is repeated and the solid is washed with hexane in order to eliminate any non-reacted TiCl 4 .
- a further method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to U.S. 4,220,554 ) and an excess of TiCl 4 comprising the internal electron donor compound in solution at a temperature of 80 to 120°C.
- the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) n-y X y , where n is the valence of titanium and y is a number between 1 and n, preferably TiCl 4 , with a magnesium chloride deriving from an adduct of formula MgCl 2 •pROH, where p is a number between 0,1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
- the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648 .
- the so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3 preferably between 0,1 and 2,5.
- the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl 4 (generally 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0,5-2 hours.
- the treatment with TiCl 4 can be carried out one or more times.
- the internal electron donor compound can be added during the treatment with TiCl 4 .
- the treatment with the electron donor compound can be repeated one or more times.
- the preparation of catalyst components in spherical form is described for example in European Patent Applications EP-A-395083 , EP-A-553805 , EP-A-553806 , EPA-601525 and WO98/44001 .
- the solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) generally between 20 and 500 m 2 /g and preferably between 50 and 400 m 2 /g, and a total porosity (by B.E.T. method) higher than 0,2 cm 3 /g preferably between 0,2 and 0,6 cm 3 /g.
- the porosity (Hg method) due to pores with radius up to 10.000 ⁇ generally ranges from 0.3 to 1.5 cm 3 /g, preferably from 0.45 to 1 cm 3 /g.
- the alkyl-Al compound (B) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt 2 Cl and Al 2 Et 3 Cl 3 .
- the external donors (C) are preferably selected among silicon compounds of formula R a 5 R b 6 Si(OR 7 ) c , where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R 5 , R 6 , and R 7 , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
- a particularly preferred group of silicon compounds is that in which a is 0, c is 3, b is 1 and R 6 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R 7 is methyl.
- Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.
- the use of thexyltrimethoxysilane is particularly preferred.
- the electron donor compound (C) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (c) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
- pre-polymerize said catalyst in a pre-polymerization step.
- Said prepolymerization can be carried out in liquid, (slurry or solution) or in the gas-phase, at temperatures generally lower than 100°C, preferably between 20 and 70°C.
- the pre-polymerization step is carried out with small quantities of monomers for the time which is necessary to obtain the polymer in amounts of between 0.5 and 2000g per g of solid catalyst component, preferably between 5 and 500 and, more preferably, between 10 and 100g per g of solid catalyst component.
- the polymerization process can be carried out according to known techniques, for example slurry polymerization using as diluent a liquid inert hydrocarbon, or solution polymerization using for example the liquid butene-1 as a reaction medium. Moreover, it may also be possible to carry out the polymerization process in the gas-phase, operating in one or more fluidized or mechanically agitated bed reactors. The polymerization carried out in the liquid butene-1 as a reaction medium is highly preferred.
- the polymerization is generally carried out at temperature of from 20 to 120°C, preferably of from 40 to 90°C.
- the polymerization can be carried out in one or more reactors that can work under same or different reaction conditions such as concentration of molecular weight regulator, comonomer concentration, temperature or pressure.
- Working in more than one reactor under different conditions can lead to the preparation of butene-1 copolymers with different average molecular weight in the two reactors and therefore with a broader molecular weight distribution optionally of bimodal type.
- working in more than one reactor under different conditions has the advantage that the various polymerization step can be properly modulated so as to properly tailoring the properties of the final polymer.
- the so obtained products show, for a given total content of comonomer, better mechanical properties, in particular higher tensile strength, with respect to the copolymers having the same total comonomer content but obtained through a single set of polymerization conditions.
- a butene-1/ethylene copolymer having a total content of ethylene units in the range of 10-25% mol can be advantageously prepared by two polymerization steps under different conditions in which in one of the step is prepared a copolymer having from less than 10% of comonomer for example 1 to 9% while in the other step another copolymer is prepared having a comonomer content higher than 10% and for example in the range 15-40%mol.
- the skilled in the art can easily adjust the mass balance between the various fractions of the blends in order to have a final content of comonomer that meets the target.
- the so obtained copolymer can have the same uses as the copolymer obtained via a single set of polymerization conditions. Accordingly, they are particularly suitable for the preparation of polymer compositions for use in applications where a certain level of softness is required.
- the copolymers of the invention are suitable for use in many applications.
- the relevant experts can add further polymer components, additives (such as stabilizers, antioxidants, anticorrosives, nucleating agents, processing and aids) and both organic and inorganic fillers which can impart specific properties, without departing from the gist of the invention.
- 13 C-NMR spectra were performed on a polymer solution (8-12 %wt) in dideuterated 1,1,2,2-tetrachloro-ethane at 120°C.
- the 13 C NMR spectra were acquired on a Bruker DPX-400 spectrometer operating at 100.61 MHz in the Fourier transform mode at 120 °C using a 90° pulse, 15 seconds of delay between pulses and CPD (WALTZ 16) to remove 1 H- 13 C coupling.
- About 1000 transients were stored in 32K data points using a spectral window of 60 ppm (0-60ppm).
- the product of reactivity ratios are obtained from 13 C NMR triad distribution according to C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 10, 536 (1977 ) using the following expressions.
- r 1 ⁇ r 2 1 + EEE + BEE BEB + 1 - B E + 1 ⁇ EEE + BEE BEB + 1 0.5
- r 1 ⁇ r 2 1 + PPP + BPP BPB + 1 - B P + 1 ⁇ PPP + BPP BPB + 1 0.5
- the isotacticity of the BBBBB pentad was evaluated from the amount of mrrm pentad (signal at 26.59 ppm) according to the following expression based on the pure "asymmetric bernoullian site" (see Two-site model analysis of 13C NMR of polypropylene polymerize by Ziegler -Natta catalyst with external alkoxysilane donors, R. Chûjô, Y. Kogure, T.
- mmmm % 100 ⁇ I mmmm / I mmmm + 5 ⁇ I mrrm
- I(mmmm) is the area of the mmmm signal at 27.73 ppm
- I(mrrm) is the area of the single unit error pentad mrrm.
- This property is strictly connected with the molecular weight distribution of the polymer under examination. In particular it is inversely proportional to the creep resistance of the polymer in the molten state. Said resistance called modulus separation at low modulus value (500 Pa), was determined at a temperature of 200°C by using a parallel plates rheometer model RMS-800 marketed by RHEOMETRICS (USA), operating at an oscillation frequency which increases from 0.1 rad/sec to 100 rad/second. From the modulus separation value, one can derive the P.I. by way of the equation: P .
- Seal initiation temperature determined by preparing 50 ⁇ m-thick films by extruding the compositions of the examples at about 200.degree. C. Each film thus obtained is laid over a plaque of polypropylene having a xylene-soluble of 4% by weight, melt flow rate of 2 g/10 min. The overlapped film and plaque are bonded in a plate-press at 200.degree. C. with a load of 9000 kg. The said load is maintained for 5 minutes. The resulting bonded test pieces are then stretched six times their length and width using a TM LONG film stretcher, thus obtaining films of a thickness of about 20 .mu.m. 5.times.10 cm specimens are obtained from the said films.
- SIT Seal initiation temperature
- the sealing values are obtained by applying a 200 g load to heat-sealed samples. For each measurement two of the above specimens are overlapped with the heat-sealable layers, made up of the compositions of the examples, touching each other. The said overlapped specimens are then sealed along the 5 cm side using a Xentinel combination laboratory sealer model 12-12 AS. The sealing time is 5 seconds, the pressure about 0.12 MPa (1.2 atm) and the width of the seals 2.5 cm. The sealing temperature is increased by 2.degree. C. for each sample to be measured.
- the sealed samples are then cut to obtain 2.5.times.10 cm strips, whose unsealed ends are attached to a dynamometer, and the minimum seal temperature where the seal does not break when a 200 g load is applied is determined. This temperature represents the seal initiation temperature
- the catalyst component contained 2.8 wt% ofTi and 12.3 wt% of phthalate.
- the copolymer was collected and dried overnight in an oven to remove all traces of water. The characterization of the copolymers is reported in Table 2. None of the copolymers showed the presence of 4,1-butene units insertion.
- copolymerization was carried out according to the procedure described in Example 1 with the only difference that propylene in the amount reported in table 3 was used instead of ethylene.
- the details regarding the amount of catalyst, the total pressure and the hydrogen used are also indicated in table 1.
- the characterization of the copolymers is reported in Table 4. None of the copolymers showed the presence of 4,1-butene units insertion.
- a five layer film of the type A/B/C/B/A having the following composition was prepared.
- a mechanical blend comprising 10%bw of the butene-1 copolymer of example 1 and 90% of an isotactic terpolymer having a SIT (Seal Initiation Temperature) of 93°C containing 0.5%wt of ethylene, 18%bw of butene-1 and 81.5% of propylene was prepared. On a film obtained from this composition was carried out the test for the determination of the SIT that resulted to be 76°C.
- SIT Serial Initiation Temperature
- Example 13 A composition as described in the Example 13 was prepared with the only difference that the butene-1 copolymer used was that of comparison example 6.
- the SIT determined on the film obtained from this composition was 84°C.
Abstract
Description
- The present invention relates to butene-1 copolymers containing up to 40% by mol of ethylene and/or propylene derived units, and to a process for their preparation.
- Butene-1 copolymers are well known in the art and have a wide range of applicability. In particular, butene-1 copolymers with a low content of comonomer (1-3%by mol) are generally characterized by good properties in terms of pressure resistance, creep resistance, impact strength and can be used in the manufacture of pipes for replacing the metal pipes. One of the key aspects for their application in the pipe sector is the excellent balance between flexibility and rigidity that they must have in order to combine easy pipe workability and mechanical resistance. In addition, butene-1 copolymers with a higher content of comonomer can be used for example as components of blends with other polyolefin or polymeric products, in order to modulate particular properties such as sealing strength, flexibility and softness of the plastic materials.
- The butene-1 copolymers can be prepared by copolymerizing butene-1 in the presence of TiCl3-based catalyst components together with diethylaluminum chloride (DEAC) as cocatalyst. The copolymers obtained by this process, however, generally do not show satisfactory properties because of the substantially non-random distribution of the comonomer in the polymer chain. Furthermore, in view of the low yields obtainable with the TiCl3 based catalysts, the butene-1 copolymers prepared with these catalysts have a high content of catalyst residues (generally more than 300 ppm of Ti) which lowers the properties of the polymers making it necessary a deashing step.
- Butene-1/propylene copolymers and a method for their preparation are described in
EP-A-353319 EP-A-353318 - Butene-1/ethylene copolymers have been disclosed also in
PCT/EP 02/06574 by using a catalyst based on metallocene compounds. However, in this kind of copolymers there is the presence of regioerrors due to 4,1 insertions of the butene-1 units. This kind of regioerrors in the polymer chain makes more difficult to tune the comonomer content of the copolymer because a 4,1 insertion can be considered equivalent to two consecutive ethylene units in the polymer chain. - Thus, it would be desirable to find new butene-1 copolymers having a complex of properties making them suitable for the various applications. We have found that this need is satisfied by butene-1 copolymers having a particular balance between isotacticity and distribution of the comonomer together with absence of 4,1 insertions of the butene-1 units.
- It is therefore an object of the present invention to provide butene-1 copolymers containing up to 40% by mol of ethylene and/or propylene derived units, characterized by the following properties, determined as described on pages 10 to 12:
- a) Product of the comonomer reactivity ratio r1·r2 ≤2;
- b) Content of butene-1 units in the form of isotactic pentads (mmmm)> 98%; and
- c) absence of 4,1 butene unit insertions.
- In particular, the copolymers object of the present invention are endowed with the following features:
- a) Product of the comonomer reactivity ratio r1·r2≤1.5 and preferably r1·r2≤1
- b) Content of butene-1 units in the form of isotactic pentads (mmmm)≥98.5% and preferably ≥ 99%; and
- c) absence of 4,1 insertions.
- Preferably, the content of (mmmm) is >99% in correspondence of r1·r2≤1. Further, the copolymers of the present invention preferably have a Polydispersity Index measured according to the method specified below, ranging from 2 to 15; more preferably ranging from 3 to 10 and in particular in the range 4-8.
- The content of ethylene or propylene derived units in the copolymers of the present invention preferably ranges from 0.1 to 35% by mol, more preferably from 0.5 to 30% by mol.
- The copolymers having a content of ethylene or propylene lower than 3% by moles and in particular lower than 2.5% can be particularly suitable for use in the pipe sector. In this case, ethylene is a preferred comonomer. Butene-1 copolymers having a comonomer content in the range of 2-15% by moles and preferably 3-12%, can be suitable also for the preparation of polymer compositions for use in low seal initiation temperature or fiber applications.
- The applicant also observed that the butene-1 copolymers according to the present invention generally become amorphous when their comonomer content, in particular when the comonomer is ethylene, is 12% by mol or higher. At these value of comonomer content in fact, a melting point is no longer detectable by carrying out thermal analysis. Moreover, the amount of fractions soluble in xylene at 0°C becomes greater than 95%. Said specific copolymers also proved to be very soft as shown by a Shore A value of lower than 70 and in certain cases lower than 50. In view of these properties, these copolymers can be used in particular as components of polymeric compositions for use in applications where a certain level of softness is required.
- Therefore, it constitutes a further object of the present invention a polymer composition comprising:
- (A) from 1 to 99% by weight of the copolymer object of the present invention; and
- (B) from 99% to 1% by weight of another polymeric component;
- In particular, (A) can be present in an amount ranging from 10 to 90% and (B) in an amount ranging from 90% to 10%. Preferably the component (B) comprises an olefin (co)polymer. In particular the component (B) can be selected from ethylene containing (co)polymers, propylene containing (co)polymers and from their mixtures.
- Particularly interesting are the polymer compositions comprising:
- (A) from 5 to 40%wt of the butene-1 copolymers of the present invention having from 1 to 15%by mol of ethylene or propylene; and
- (B) from 60 to 95%wt of a propylene copolymer containing from 1 to 30 % by mol of ethylene and/or an α-olefin of formula CH2=CHR, where R is a C2-C10 hydrocarbon group; said percentages being based on the sum of (A)+(B).
- Preferably, said α-olefin is butene-1. Particularly interesting are the compositions in which (B) is selected from (a) a propylene copolymer containing both ethylene and butene-1 wherein the content of ethylene is from 1 to 10% and the content of butene-1 is from 1 to 10% and (b) a propylene copolymer containing from 2 to 15% by mol of butene-1.
- Said compositions, which are particularly useful in applications where a low seal initiation temperature (SIT) is required, show better performances, in terms of SIT and mechanical properties, with respect to the compositions in which butene-1 copolymers of the prior art are used.
- Interesting results have also been obtained by using the copolymers of the invention in the preparation of polymer compositions to be used in applications requiring a specific range of peel force between two layers that have been previously sealed (Seal-Peel applications). Generally, these formulations comprise:
- (i) from 5 to 25% wt of the butene-1 copolymer of the invention and
- (ii) from 75 to 95%wt of an ethylene polymer; said percentages being based on the sum of (i)+(ii).
- The ethylene polymer can be an ethylene homopolymer or copolymer. In particular, it can be selected from branched ethylene homo or copolymers obtained through high pressure high temperature radical initiated polymerization (LDPE), linear ethylene homo or copolymers with alpha-olefins having from 4 to 10 carbon atoms (HDPE or LLDPE) obtained through the use of the well known coordination catalysts such as the Ziegler-Natta catalysts or mixtures thereof.
- Also in this case the compositions containing the copolymers of the invention have shown better performances, in terms of peel performances, with respect to the compositions in which butene-1 copolymers of the prior art are used.
- The butene-1 copolymers of the present invention can be prepared by polymerization of the monomers in the presence of a stereospecific catalyst comprising (A) a solid component comprising a Ti compound and an internal electron-donor compound supported on MgCl2; (B) an alkylaluminum compound and, optionally, (C) an external electron-donor compound. Magnesium dichloride in active form is preferably used as a support. It is widely known from the patent literature that magnesium dichloride in active form is particularly suited as a support for Ziegler-Natta catalysts. In particular,
USP 4,298,718 andUSP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that the magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line. - The preferred titanium compounds used in the catalyst component of the present invention are TiCl4 and TiCl3; furthermore, also Ti-haloalcoholates of formula Ti(OR)n-yXy, where n is the valence of titanium, X is halogen, preferably chlorine, and y is a number between 1 and n, can be used.
- The internal electron-donor compound is preferably selected from esters and more preferably from alkyl, cycloalkyl or acryl esters of monocarboxylic acids, for example benzoic acids, or polycarboxylic acids, for example phthalic or succinic acids, the said alkyl, cycloalkyl or aryl groups having from 1 to 18 carbon atoms. Examples of the said electron-donor compounds are diisobutyl phthalate, diethylphtahalate and dihexylphthalate. Generally, the internal electron donor compound is used in molar ratio with respect to the MgCl2 of from 0.01 to 1 preferably from 0.05 to 0.5.
- The preparation of the solid catalyst component can be carried out according to several methods.
- According to one of these methods, the magnesium dichloride in an anhydrous state and the internal electron donor compound are milled together under conditions in which activation of the magnesium dichloride occurs. The so obtained product can be treated one or more times with an excess of TiCl4 at a temperature between 80 and 135°C. This treatment is followed by washings with hydrocarbon solvents until chloride ions disappeared. According to a further method, the product obtained by co-milling the magnesium chloride in an anhydrous state, the titanium compound and the internal electron donor compound is treated with halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene or dichloromethane. The treatment is carried out for a time between 1 and 4 hours and at temperature of from 40°C to the boiling point of the halogenated hydrocarbon. The product obtained is then generally washed with inert hydrocarbon solvents such as hexane.
- According to another method, magnesium dichloride is pre-activated according to well known methods and then treated with an excess of TiCl4 at a temperature of 80 to 135°C which contains, in solution, an internal electron donor compound. The treatment with TiCl4 is repeated and the solid is washed with hexane in order to eliminate any non-reacted TiCl4.
- A further method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to
U.S. 4,220,554 ) and an excess of TiCl4 comprising the internal electron donor compound in solution at a temperature of 80 to 120°C. - According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR)n-yXy, where n is the valence of titanium and y is a number between 1 and n, preferably TiCl4, with a magnesium chloride deriving from an adduct of formula MgCl2•pROH, where p is a number between 0,1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in
USP 4,399,054 andUSP 4,469,648 . The so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3 preferably between 0,1 and 2,5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4 (generally 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0,5-2 hours. The treatment with TiCl4 can be carried out one or more times. The internal electron donor compound can be added during the treatment with TiCl4. The treatment with the electron donor compound can be repeated one or more times. The preparation of catalyst components in spherical form is described for example in European Patent ApplicationsEP-A-395083 EP-A-553805 EP-A-553806 EPA-601525 WO98/44001 - The solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) generally between 20 and 500 m2/g and preferably between 50 and 400 m2/g, and a total porosity (by B.E.T. method) higher than 0,2 cm3/g preferably between 0,2 and 0,6 cm3/g. The porosity (Hg method) due to pores with radius up to 10.000Å generally ranges from 0.3 to 1.5 cm3/g, preferably from 0.45 to 1 cm3/g.
- The alkyl-Al compound (B) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use mixtures of trialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and Al2Et3Cl3.
- The external donors (C) are preferably selected among silicon compounds of formula Ra 5Rb 6Si(OR7)c, where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R5, R6, and R7, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. A particularly preferred group of silicon compounds is that in which a is 0, c is 3, b is 1 and R6 is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and R7 is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane. The use of thexyltrimethoxysilane is particularly preferred.
- The electron donor compound (C) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (c) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
- In order to make the catalyst particularly suitable for the polymerization step, it is possible to pre-polymerize said catalyst in a pre-polymerization step. Said prepolymerization can be carried out in liquid, (slurry or solution) or in the gas-phase, at temperatures generally lower than 100°C, preferably between 20 and 70°C. The pre-polymerization step is carried out with small quantities of monomers for the time which is necessary to obtain the polymer in amounts of between 0.5 and 2000g per g of solid catalyst component, preferably between 5 and 500 and, more preferably, between 10 and 100g per g of solid catalyst component.
- The polymerization process can be carried out according to known techniques, for example slurry polymerization using as diluent a liquid inert hydrocarbon, or solution polymerization using for example the liquid butene-1 as a reaction medium. Moreover, it may also be possible to carry out the polymerization process in the gas-phase, operating in one or more fluidized or mechanically agitated bed reactors. The polymerization carried out in the liquid butene-1 as a reaction medium is highly preferred.
- The polymerization is generally carried out at temperature of from 20 to 120°C, preferably of from 40 to 90°C. The polymerization can be carried out in one or more reactors that can work under same or different reaction conditions such as concentration of molecular weight regulator, comonomer concentration, temperature or pressure. Working in more than one reactor under different conditions can lead to the preparation of butene-1 copolymers with different average molecular weight in the two reactors and therefore with a broader molecular weight distribution optionally of bimodal type. Moreover, working in more than one reactor under different conditions has the advantage that the various polymerization step can be properly modulated so as to properly tailoring the properties of the final polymer. This technique has proved to be very effective for solving the operative problems involved with the preparation of the copolymers of the invention with a comonomer content of 10% by moles or higher. These products in fact, can give problems during certain operations such as pelletization. The applicant has surprisingly found that if the butene copolymer having a final comonomer content of 10% or higher is obtained through a copolymerization carried out in two or more reactors in series operating under conditions such that in at least one of them is produced a copolymer fraction having a detectable melting temperature, the above operative problems are minimized or fully solved.
- In addition, the so obtained products show, for a given total content of comonomer, better mechanical properties, in particular higher tensile strength, with respect to the copolymers having the same total comonomer content but obtained through a single set of polymerization conditions. For example, a butene-1/ethylene copolymer having a total content of ethylene units in the range of 10-25% mol can be advantageously prepared by two polymerization steps under different conditions in which in one of the step is prepared a copolymer having from less than 10% of comonomer for example 1 to 9% while in the other step another copolymer is prepared having a comonomer content higher than 10% and for example in the range 15-40%mol. Depending on the desired kind of properties the skilled in the art can easily adjust the mass balance between the various fractions of the blends in order to have a final content of comonomer that meets the target. The so obtained copolymer can have the same uses as the copolymer obtained via a single set of polymerization conditions. Accordingly, they are particularly suitable for the preparation of polymer compositions for use in applications where a certain level of softness is required.
- As mentioned above, the copolymers of the invention are suitable for use in many applications. As a customary routine, for each of these applications the relevant experts can add further polymer components, additives (such as stabilizers, antioxidants, anticorrosives, nucleating agents, processing and aids) and both organic and inorganic fillers which can impart specific properties, without departing from the gist of the invention.
- The following examples are given in order to better illustrate the invention without limiting it.
- 13C-NMR spectra were performed on a polymer solution (8-12 %wt) in dideuterated 1,1,2,2-tetrachloro-ethane at 120°C. The 13C NMR spectra were acquired on a Bruker DPX-400 spectrometer operating at 100.61 MHz in the Fourier transform mode at 120 °C using a 90° pulse, 15 seconds of delay between pulses and CPD (WALTZ 16) to remove 1H-13C coupling. About 1000 transients were stored in 32K data points using a spectral window of 60 ppm (0-60ppm).
- The ethylene content was obtained from the triad distribution ([E] = [EEE]+[EEB]+[BEB]) which is calculated as:
BBB = (C-2I)/Σ BBE = B/Σ EBE = L/Σ BEB =I/Σ BEE= D/Σ EEE = (0.25F+0.5G)/Σ - B, C, D, F, G, I, L are the integrals of the peaks in the 13C NMR spectrum (peak of EEE sequence at 29.9 ppm as reference). The assignment of these peaks are made according to J.C. Randall, Macromol. Chem Phys., C29, 201 (1989) and are reported in Table A (nomenclature according to C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 10, 536 (1977)).
Table A. Area Chemical Shift Assignments Sequence B 37.24 Tβδ BBE 35.20-34.88 Tββ BBB C 34.88-34.49 Sαγ BBEB+BEBE D 34.49-34.00 Sαδ EBEE+BBEE F 30.39 Sγδ BEEE G 29.9 Sδδ EEE I 24.54-24.24 Sββ BEB L 11.22 Tδδ EBE - The propylene content was obtained from the triad distribution ([P] = [PPP]+[PPB]+[BPB]) which is calculated as:
BBB = M/Σ BBP = L/Σ PBP = I/Σ BPB = 0.5 D/Σ BPP= ⅓ (A+0.5 (B+E)+2 A+B+E)/Σ PPP = (C+0.5B)/Σ - Where Σ = M +L+I+0.5D+ ⅓ (A+0.5 (B+E)+2 A+B+E)+ (C+0.5B) and A, B, C, D, E, I, L, M are the integrals of the peaks in the 13C NMR spectrum (The peak at 27.73 ppm due the CH2 carbon in the branch of an isotactic BBBBB pentad is used as internal reference). The assignment of these peaks are made according to H.N. Cheng, Journal of Polymer Science, Polymer Physics Edition, 21, 573 (1983) and are reported in Table B (nomenclature according to C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 10, 536 (1977)).
Table B Area Chemical Shift Assignments Sequence A 47.15 CH2 chain BPPB B 46.83 CH2 chain PPPB C 46.52 CH2 chain PPPP D 43.67 CH2 chain BPBX E 43.37 CH2 chain PPBX I 28.13 CH2 branch PBP L 27.93 CH2 branch BBP M 27.73 CH2 branch BBB - The product of reactivity ratios are obtained from 13C NMR triad distribution according to C.J. Carman, R.A. Harrington and C.E. Wilkes, Macromolecules, 10, 536 (1977) using the following expressions.
-
-
- The assignment of the pentad signals in the region of branch methylene carbons was made according to Carbon-13 NMR Spectral Assignment of Five Polyolefins Determined from the Chemical Shift Calculation and the Polymerization Mechanism, T. Asakura and others, Macromolecules 1991, 24 2334-2340 .
- Due to the superimposition between stereoirregular pentads and peaks from either BBE / EBE or BBP / PBP sequences, the isotacticity of the BBBBB pentad was evaluated from the amount of mrrm pentad (signal at 26.59 ppm) according to the following expression based on the pure "asymmetric bernoullian site" (see Two-site model analysis of 13C NMR of polypropylene polymerize by Ziegler -Natta catalyst with external alkoxysilane donors, R. Chûjô, Y. Kogure, T. Väänänen, Polymer, 1994, 35, 339-342 ):
Where I(mmmm) is the area of the mmmm signal at 27.73 ppm and I(mrrm) is the area of the single unit error pentad mrrm. - In the case of either butene homopolymers or butene/propylene copolymers the amount of 4,1 inserted butene units is determined via 13C NMR spectroscopy using the above-mentioned experimental conditions. Assignments of 4,1 inserted units are made according to V. Busico, R. Cipullo, A. Borriello, Macromol. Rapid. Commun. 16, 269, (1995).
- The content of 4,1 insertions is calculated as:
Q and B are the integrals of the signals reported in Table B (The peak at 27.73 ppm due the CH2 carbon in the branch of an isotactic BBBBB pentad is used as internal reference).Table B Integral Chemical Shift
(ppm)Carbon Sequence B 40.21 CH2 (Sαα) B Q 37.3 CH -CH(CH2CH3)-(CH2)5-CH(CH2CH3)- - The percentage of the 4,1 inserted butene units in the case of butene/ethylene copolymers is assumed to be the same as that obtained for the butene-1 homopolymers prepared under identical polymerization conditions apart from the absence of comonomer.
- This property is strictly connected with the molecular weight distribution of the polymer under examination. In particular it is inversely proportional to the creep resistance of the polymer in the molten state. Said resistance called modulus separation at low modulus value (500 Pa), was determined at a temperature of 200°C by using a parallel plates rheometer model RMS-800 marketed by RHEOMETRICS (USA), operating at an oscillation frequency which increases from 0.1 rad/sec to 100 rad/second. From the modulus separation value, one can derive the P.I. by way of the equation:
in which the modulus separation is defined as:
wherein G' is storage modulus and G" is the loss modulus. - Measured according to ASTM D2240
- Measured according to ASTM-D638 on a 1:9 mm thick plaque obtained by compression molding (at 200°C with an cooling of 30°/min) of a polymer composition obtained by mixing in a Brabender the relevant copolymer sample with 1 % 2,6- di-t-butyl-4-methyl phenol (BHT) at 180°C.
- Seal initiation temperature (SIT): determined by preparing 50 µm-thick films by extruding the compositions of the examples at about 200.degree. C. Each film thus obtained is laid over a plaque of polypropylene having a xylene-soluble of 4% by weight, melt flow rate of 2 g/10 min. The overlapped film and plaque are bonded in a plate-press at 200.degree. C. with a load of 9000 kg. The said load is maintained for 5 minutes. The resulting bonded test pieces are then stretched six times their length and width using a TM LONG film stretcher, thus obtaining films of a thickness of about 20 .mu.m. 5.times.10 cm specimens are obtained from the said films. The sealing values are obtained by applying a 200 g load to heat-sealed samples. For each measurement two of the above specimens are overlapped with the heat-sealable layers, made up of the compositions of the examples, touching each other. The said overlapped specimens are then sealed along the 5 cm side using a Xentinel combination laboratory sealer model 12-12 AS. The sealing time is 5 seconds, the pressure about 0.12 MPa (1.2 atm) and the width of the seals 2.5 cm. The sealing temperature is increased by 2.degree. C. for each sample to be measured. The sealed samples are then cut to obtain 2.5.times.10 cm strips, whose unsealed ends are attached to a dynamometer, and the minimum seal temperature where the seal does not break when a 200 g load is applied is determined. This temperature represents the seal initiation temperature
-
- 1 Sealing. The film to be tested is cut (MD direction) to samples having a width of 150 mm and a length of 200 mm. Pieces of a 400 µm thick film of the same polymer used for the support layer are cut in the same dimensions, thereby obtaining substrate pieces. Both the samples of films to be tested and the substrate pieces are put between the sealing bars of a KOPP SPGE 20 laboratory sealing machine, with the samples on the top. The upper sealing bar is heated up to the sealing temperature. The sealing bars are closed for 1 second under a pressure of 1.6 bar and seals are produced (100 mm length, 10 mm weld overlap) in the TD direction. The temperatures at which the samples are sealed to the substrate pieces are reported in Table 1.
- 2. Peel Test After conditioning the sealed samples for 24 hours at 23.degree. C., the peel strength is tested with an Instron machine. The samples and the substrate pieces to which they are sealed are first cut to test samples having a width of 15 mm and are then clamped between grips with a grip distance of 50 mm. The force needed to pull open the seal with a constant speed of 50 mm/min. is recorded. Such force, expressed in N/15 mm, corresponds to the peel strength and is reported, for each sample, in Table 1.
- Into a 500 ml four-necked round flask, purged with nitrogen, 225 ml of TiCl4 were introduced at 0°C. While stirring, 6.8 g of microspheroidal MgCl2·2.7C2H5OH (prepared as described in Ex. 2 of
USP 4,399,054 but operating at 3,000 rpm instead of 10,000) were added. The flask was heated to 40°C and 4.4 mmoles of diisobutylphthalate were thereupon added. The temperature was raised to 100°C and maintained for two hours, then stirring was discontinued, the solid product was allowed to settle and the supernatant liquid was siphoned off. 200 ml of fresh TiCl4 were added, the mixture was reacted at 120°C for one hour then the supernatant liquid was siphoned off and the solid obtained was washed six times with anhydrous hexane (6 x 100 ml) at 60°C and then dried under vacuum. The catalyst component contained 2.8 wt% ofTi and 12.3 wt% of phthalate. - In a 4 liter autoclave, purged with nitrogen flow at 70 °C for one our. 1350 g of butene-1, an amount of ethylene as indicated in table 1 and hydrogen as indicated in table 1 were added. The temperature was raised to nearly 75°C and a pre-reacted mixture containing 75 ml of anhydrous hexane containing 1.4 g of AliBu3, and thexyltrimethoxysilane (Al/ thexyltrimethoxysilane molar ratio of 40) and an amount, indicated in table 1, of solid catalyst prepared as reported above were introduced in nitrogen flow to start the reaction. The total internal pressure was measured and maintained constant for the whole copolymerization time by continuously feeding ethylene. The amount of ethylene fed in this period is reported in Table 1.
- After 2 hours the reaction is stopped by discharging the liquid phase (all the prepared copolymers were completely soluble in 1-butene at 75 °C) in an excess of water.
- The copolymer was collected and dried overnight in an oven to remove all traces of water. The characterization of the copolymers is reported in Table 2. None of the copolymers showed the presence of 4,1-butene units insertion.
- The preparation of the butene-1-ethylene copolymer described in example 2 of
EP-A-353318 - The copolymerization was carried out according to the procedure described in Example 1 with the only difference that propylene in the amount reported in table 3 was used instead of ethylene. The details regarding the amount of catalyst, the total pressure and the hydrogen used are also indicated in table 1. The characterization of the copolymers is reported in Table 4. None of the copolymers showed the presence of 4,1-butene units insertion.
- The sequential polymerization was carried out in two liquid-phase stirred reactors connected in series in which liquid butene-1 constituted the liquid medium. The same catalyst system described in the previous examples was injected into the first reactor working under the following conditions:
- Temperature (°C): 75°C
- Ethylene/Butene feed ratio= abt. 5%
- Hydrogen/Butene feed ratio= abt 1200 ppm vol
- After 2 hours of polymerization the content of the first reactor was transferred into the second reactor where the polymerization continued under the same conditions with the only difference that the ethylene feed was discontinued. The polymerization was stopped after 70 minutes and the final copolymer was characterized. On the basis of the polymerization activity about 70% of the total copolymer was produced in the first polymerization step and showed an ethylene content of 12.2%wt. The remaining 30%, produced in the second reactor, had a calculated ethylene content of 1.6%wt. The ethylene content of the final product is therefore about 9%. The results of the characterization carried out on the final copolymer are reported in Table 5.
- A five layer film of the type A/B/C/B/A having the following composition was prepared.
- (A) Seal/Peel layer (15µm) comprising 65% low density polyethylene having a Melt Index of 1.5 and a density of 0.919; 25% of a linear low density polyethylene (MIE 1; density 0.919) and 15% of the butene-1 copolymer produced as described in Example 1.
- (C) Core layer (40 µm) constituted by a linear low density polyethylene (MIE 1; density 0.936)
- (B) Backbone layer (15µm) constituted by a low density polyethylene (MIE 0.9; density 0.93)
- The film was tested for determination of Peel strength according to the method reported above. The results are shown in Table 6.
- A mechanical blend comprising 10%bw of the butene-1 copolymer of example 1 and 90% of an isotactic terpolymer having a SIT (Seal Initiation Temperature) of 93°C containing 0.5%wt of ethylene, 18%bw of butene-1 and 81.5% of propylene was prepared. On a film obtained from this composition was carried out the test for the determination of the SIT that resulted to be 76°C.
- A composition as described in the Example 13 was prepared with the only difference that the butene-1 copolymer used was that of comparison example 6. The SIT determined on the film obtained from this composition was 84°C.
Table 1 Ex Catalyst Ptotal Ethylene Yield mg Bar-g Ga gb Kg/gcat 1 6.5 11.5 3.0 13.4 39.2 2 5.9 11.8 6.0 16.5 22.0 3 5.3 11.9 11.5 39.4 54.7 4 5.8 12.4 20.0 39.0 42.2 5 5.2 13.2 20 53 44.2 a Ethylene added before the injection of the catalyst.
b Ethylene added during the copolymerization in order to keep constant the autoclave pressure.Table 2 Ex X.S.1 [η]2 C2- r 1 r 2 Tm ΔH Tg PI Mmmm Tens. Strength Tens. Mod. 23° Shore A %wt dL/g Mol% °C J/g °C % MPa MPa 1 25.0 1.85 2.1 0.8 91.2 19.2 -34 4 99.3 38.3 290 nm 2 96.9 1.75 12.4 0.9 nd- - -40 3.9 99.2 14.6 70 75 3 95.6 2.46 19.5 1.0 nd- - -42 3.8 99.1 5.8 10.1 45 4 96.2 2.39 29.5 0.9 nd- - -46 3.8 99.3 2.6 3.7 29 5 99.2 1.92 34.2 0.94 nd- - - nm 99.3 3.6 7.1 34 6 * 80 1.9 4.3 0.8 nd- - - nm 97.1 30 160 nm nd = not detectable
nm= not measured
1 Xylene Soluble at 0°C; 2 Intrinsic viscosity in THN;
* ComparativeTable 3 Ex Catalyst Ptotal Propylene Yield mg Bar-g Ga gb Kg/gcat 7 11.5 12 3.0 50 38.3 8 6.7 12 6.0 26.4 43.3 9 17 13.2 96.3 42.7 42.6 10 11 13.2 96 82.0 40.2 a Ethylene added before the injection of the catalyst.
b Ethylene added during the copolymerization in order to keep constant the autoclave pressure.Table 4 Ex X.S.1 [η] 2 Propylene r 1 r 2 Tm ΔH Tg mmmm Tens. Mod.
(1-3% chord)%wt dL/g Mol% °C J/g °C % MPa 7 1.2 2.41 0.6 1.2 125 19.2 -34 99.1 286 8 2 1.95 3.3 1.3 124 - -40 98.6 9 22 2.25 9.7 1.5 120 - -42 98.9 10 97.6 1.7 18.1 1.7 112 - -46 99.2 200 1 Xylene Soluble at 0°C; 2 Intrinsic viscosity in THN Table 5 Ex 3C2- Tm ΔH TS
At breakTM23° Shore A Mol% °C J/g MPa MPa 11 16.6 90 6 5.6 20 72
Claims (27)
- Butene-1 copolymers containing up to 40% by mol of ethylene and/or propylene derived units, characterized by the following properties determined by 13C NMR spectra acquired on a 400 MHz spectrometer operating at 100.61 MHz of 120°C:a) Product of the reactivity ratios obtained from 13C NMR triad distribution is r1·r2 ≤ 2;b) Content of butene-1 units in form of isotactic pentads evaluated according to the following expression:
wherein I(mmmm) is the area of the mmmm signal at 27.73 ppm and I(mrrm) is the area of the single unit error pentad mrrm; andc) absence of 4,1 insertions of butene units. - The butene-1 copolymers according to claim 1 in which the mmmm% is > 99% in correspondence of r1•r2 ≤ 1.
- The butene-1 copolymers according to claim 1 characterized by the following features:a) reactivity ratio r1•r2 ≤ 1.5;b) Content of butene-1 units in the form of isotactic pentads (mmmm)> 98.5%; andc) absence of 4,1 insertions.
- The butene-1 copolymer according to claim 3 having a Polydispersity Index in the range 3-10.
- The butene-1 copolymers according to claim 1 having a content of ethylene and/or propylene derived units ranging from 0.1 to 35% by mol.
- The butene-1 copolymers according to claim 5 having a content of ethylene and/or propylene derived units ranging from 0.5 to 30% by mol.
- The butene-1 copolymers according to claim 6 wherein the comonomer is ethylene.
- The butene-1 copolymers according to claim 6 wherein the comonomer is propylene.
- The butene-1 copolymers according to claim 6 having a content of ethylene or propylene lower than 3%.
- The butene-1 copolymers according to claim 6 having a content of ethylene and/or propylene in the range of 2-15%.
- The butene-1 copolymers according to claim 6 having a content of ethylene or propylene derived units equal to, or higher than, 12%.
- The butene-1 copolymers according to claim 11 in which the comonomer is ethylene.
- The butene-1 copolymers according to claim 11 characterized by the fact that they do not show a melting point at the thermal analysis.
- A polymer composition comprising (A) from 1 to 99wt % of a butene-1 copolymer according to claim 1 and (B) from 1 to 99% of another polymeric component the said percentages being referred to the sum of (A) and (B).
- A polymer composition according to claim 14 in which the component (B) comprises an olefin (co)polymer.
- A polymer composition according to claim 14 in which the component (B) is a ethylene containing (co)polymer, a propylene containing (co)polymer or their mixtures.
- A polymer composition comprising:(A) from 5 to 40%wt of the butene-1 copolymers according to claim 1 having from 1 to 15%by mol of ethylene or propylene; and(B) from 60 to 95%wt of a propylene copolymer containing from 1 to 30 % by mol of ethylene and/or an α-olefin of formula CH2=CHR, where R is a C2-C10 hydrocarbon group.
- A polymer composition according to claim 17 in which said α-olefin is butene-1.
- A polymer composition according to claim 18 in which the component (B) is selected from either (a) a propylene copolymer containing both ethylene and butene-1 wherein the content of ethylene is from 1 to 10% and the content of butene-1 is from 1 to 10% or (b) a propylene copolymer containing from 2 to 15% by mol of butene-1.
- A polymer composition comprising (A) a butene-1 copolymer according to claim 1 not showing a melting point and (B) a butene-1 copolymer according to claim 1 showing a melting point.
- A polymer composition according to claim 20 in which (A) is a butene-1/ethylene copolymer having a content of ethylene of higher than 10% and (B) is a butene-1/ethylene copolymer having a content of ethylene of less than 10%by mol.
- A polymer composition comprising :(i) from 5 to 25% wt of the butene-1 copolymer according to any of claims 1-13 and(ii) from 75 to 95%wt of an ethylene polymer; said percentages being based on the sum of (i)+(ii).
- Manufactured articles obtained from the butene-1 copolymers or their blends according to any of the preceding claims.
- Process for the preparation of the butene-1 copolymers according to any of claims 1-12 comprising copolymerizing butene-1 and ethylene and/or propylene in the presence of a stereospecific catalyst comprising (A) a solid catalyst component comprising a Ti compound and an electron-donor compound selected from phthalates, supported on MgCl2; (B) an alkylaluminum compound and, (C) an external electron-donor compound of formula Ra 5Rb 6Si(OR7)c, where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R5, R6, and R7, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
- The process according to claim 24 wherein the external donor is thexyttrimethoxysilane.
- Process according to claim 24 or 25 carried out in liquid butene-1.
- Process according to claim 26 in which the co-polymerization is carried out in at least two reactors working under different reaction conditions.
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- 2003-11-03 JP JP2005510224A patent/JP4971633B2/en not_active Expired - Lifetime
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CN1717423A (en) | 2006-01-04 |
AU2003287991A1 (en) | 2004-06-18 |
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JP2006508237A (en) | 2006-03-09 |
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CA2506650A1 (en) | 2004-06-10 |
RU2005120245A (en) | 2006-01-20 |
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US20110136981A1 (en) | 2011-06-09 |
AR042144A1 (en) | 2005-06-08 |
RU2318833C2 (en) | 2008-03-10 |
BRPI0315946B8 (en) | 2016-05-17 |
CN100491421C (en) | 2009-05-27 |
EP1565502A1 (en) | 2005-08-24 |
JP4971633B2 (en) | 2012-07-11 |
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